Daglen, Bevin Colleen, 1977-
2009-02-18T00:14:23Z
2009-02-18T00:14:23Z
2008-09
http://hdl.handle.net/1794/8567
xxii, 143 p. ; ill. (some col.) A print copy of this title is available through the UO Libraries. Search the library catalog for the location and call number.
There are compelling economic and environmental reasons for using degradable plastics in selected applications and considerable research is now devoted to devising new photodegradable polymers with improved performance. Controlling the degradation of these materials in a prescribed fashion is still a difficult problem because the parameters that influence degradation rates are not completely understood. In order to predict polymer lifetimes, to manipulate when a polymer starts to degrade, and to control the rate of degradation, it is necessary to identify the experimental parameters that affect polymer degradation rates and to understand how these parameters affect degradation.
This dissertation describes the results of experiments designed to gain fundamental insight into the factors that affect the rate of polymer photodegradation. The key experimental strategy employed was the incorporation of organometallic dimers into the backbone of the polymer chains, specifically, [CpRMo(CO) 3 ] 2 (CpR = a substituted cyclopentadienyl (· 5 -C 5 H 4 R)). Incorporating these organometallic units into a polymer chain make the polymer photodegradable because the metal-metal bond can be cleaved with visible light. The photogenerated metal radicals can then be trapped by O 2 or chlorine, resulting in degradation of the polymer. Another benefit from incorporating this chromophore into the polymer backbone is that it provides the experimentalist with a convenient spectroscopic handle to monitor degradation rates.
Using these model polymers, several experimental factors that can affect polymer photodegradation rates have been explored. For example, experiments showed that radical trap concentration affects degradation rates below, but not above, the polymer glass transition temperature. In addition, degradation rates as a function of irradiation temperature, tensile stress, and time-dependent morphology changes were explored for various polymers. The results of these studies suggest that the ability of the photogenerated radicals to escape the radical cage is the dominant factor in determining photodegradation efficiencies.
This dissertation includes previously published and unpublished co-authored material.
Adviser: David R. Tyler
en_US
University of Oregon
University of Oregon theses, Dept. of Chemistry, Ph. D., 2008;
Photodegradation
Polymer chemistry
Organometallic polymers
Molybedum
Carbon monoxide
Cyclopentadienyl
Factors affecting the photodegradation rates of polymers that contain (cyclopentadienyl-(carbon monoxide)-molybdenum) in the backbone
Thesis